氮掺杂纳米ZnO的制备及其抗菌防紫外性研究
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摘要
晶体材料的电、磁、声、光、热和力学性能,都具有结构敏感性。晶体缺陷对晶体结构具有巨大的影响,掺杂是获得晶体缺陷的有效手段。
通过特殊元素完成对纳米晶氧化物的掺杂取代、促进晶体材料的结构敏感性的研究近来已被广泛关注。如何控制缺陷的形成、类型及变化已成为晶体材料领域研究的重要课题。
本文以Zn(NO_3)_2·6H_2O、尿素为原料,通过燃烧法,实现纳米ZnO的瞬态氮掺杂。在此基础上对晶体缺陷化学—热力学公式和晶体化学原理进行理论上研究,计算理论绝热燃烧火焰温度,完成了氮掺杂纳米氧化锌的优化设计。
通过X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)、红外光谱(IR)、光电子能谱(XPS)对粉体进行表征,研究制备过程中影响纳米氮掺杂ZnO性能的各种因素,借助差热分析对制备机理进行探讨。在此基础上,通过对氮掺杂纳米ZnO的偶联剂改性,获得稳定的氮掺杂纳米ZnO分散乳液。参照FZ/T 73023—2006中国人民共和国纺织行业标准——抗菌针织品及AATCC 183-2004紫外辐射通过织物的透射或阻挡性能,系统研究了氮掺杂纳米ZnO对纺织品的抗菌、防紫外性能。
主要研究工作和成果如下:
①瞬态氮掺杂过程中,尿素既是燃料为掺杂反应提供能量,又是氮源。同时分解所释放气体的膨胀效应,实现了微晶间的有效阻聚。完成了传统工艺中制备、陈化、洗涤、干燥、煅烧、研磨等多道工序的减并,制备出高性能氮掺杂纳米级粉色ZnO粉体。
②利用热力学公式对理论绝热燃烧火焰温度进行了计算,得到最佳工艺优化:燃料与物料摩尔比4.920;环境温度800℃;Zn(NO_3)_2·6H_2O水溶液的浓度60g/L。通过此种工艺所得到的粉体综合性能最好,平均粒度为30nm,氮掺量为1.02%,晶相与标准立方相ZnO衍射峰完全一致,没有其他杂相出现,颜色为均匀的粉色。
③改性过程中,以多羟基化合物三乙醇胺为桥基,对氮掺杂纳米ZnO进行表面预修饰,增加纳米粒子表面的羟基基团,在水介质中采用球磨工艺实施硅烷偶联剂改性,减少分散过程的软团聚,获得高浓度氮掺杂纳米ZnO水性分散浆料。
④经氮掺杂纳米ZnO整理过的棉织物,紫外防护因子测试结果表明:UPF指数从4.5提升至52,并具有较好的水洗牢度,水洗20次仍然保持同样的抗紫外性。
⑤抗菌性不受环境影响,即使在无光情况下也表现出极好的抗菌性能,且抑菌圈、抑菌率实验及氮掺杂纳米氧化锌整理后的织物抑菌率达到99%。并结合琼脂球面扩散动力学理论,指导抑菌圈实际测试,解释氮掺杂纳米ZnO抑菌机理。
本文首次提出利用燃烧法完成纳米ZnO的瞬态氮掺杂,实现传统工艺中制备、陈化、洗涤、干燥、煅烧、研磨等多道工序的减并,具有节能、降耗、减排的优点。氮掺杂纳米ZnO在纺织领域的应用填补了该产品在纺织领域的应用空白,为纺织用抗菌、抗紫外功能剂提供了新品种。
Recently, much attention has been focused on the modification of nanocrystallite metal oxide by doping or substituting with special atom. With such modification, it is possible to improve the electrical and optical properties of materials by changing the surface properties, such as electronic band gap, O vacancies, crystal deficiencies and specific surface area (SSA).
In the paper, N-doped ZnO (ZNO) nanocrystalline were synthesized by deflagration method using urea as main fuel, surfactant as assistant fuel and zinc nitrate as oxidant. The variation of adiabatic flame temperature (Tad) with the various fuel-to-oxidizer molar ratios value was calculated theoretically according to the thermodynamic concept. The effects of environment temperature, molar ratio of urea-to-zinc nitrate and combustion time on the properties of nanopowder were investigated. XRD, FTIR, SEM, TEM and XPS were used to characterize the properties of the as-synthesized samples. The ultraviolet prevention and antimicrobial properties on cotton fabrics treated by N-doped nano-ZnO were studied.
The main research work and results are as follows:
(1) During preparing N-doped nano-ZnO, The action of urea not only offered the energy, but also was the source of nitrogen. The effective inhibition effect between crystallites was realized by the expansion effect of gas released by urea. The combustion is a simplification of multi-procedures, such as traditional preparation, aging, dryinh, calcinating processes and rubbing. The N-doped ZnO (ZNO) nanocrystalline with excellent performance were synthesized by this method.
(2) The variation of adiabatic flame temperature (Tad) with the various fuel-to-oxidizer molar ratios value was calculated theoretically according to the thermodynamic concept. The experimental results show that perfect pink powders with standard cubic ZnO crystal phase are obtained under 800℃when the urea-to-zinc nitrate molar ratio is 4.920 and the concentration of the zinc nitrate is 60g/L.The average primary granularity of the as-synthsized sample is about 30 nm estimated according to Scherrer Equation. The analysises of XPS indicates that the concentrantion of N-doped in the sample is 1.02%.
(3) In this paper, well-dispersed N-doped ZnO (ZNO) nanocrystalline slurry in water medium with high concentration was prepared through the coordination action using silane coupling agent and multi-hydroxy compound. The results reveal that the N-doped ZnO (ZNO) nanocrystalline modified by multi-hydroxy compound in advance has strong combination ability with silane couple agent. Modified N-doped ZnO (ZNO) nanocrystalline has small size, even distribution and well-disperse stability.
(4) UPF test results indicate the perfect ultraviolet prevention, A high washing fastness is also attained. The index of UPF is from 4.5 to 52.
(5) The antibacterium-circle test indicate the broad-spectrum antibacterial activities. Specially, the antibacterial activities are very good even without light irradiation.
In this paper, the N-doped ZnO (ZNO) nanocrystalline with excellent performance were synthesized by combustion for the first time. The combustion is a simplification of multi-procedures, such as traditional preparation, aging, drying, calcinating processes and rubbing. Moreover, the systemic research about the antibacterium and ultraviolet prevention of the N-doped ZnO on textile was for the first. The excellent antibacterium and ultraviolet prevention properties will make N-doped ZnO nanocrystallites become a replaceable and cheap functional agent for textile.
通过特殊元素完成对纳米晶氧化物的掺杂取代、促进晶体材料的结构敏感性的研究近来已被广泛关注。如何控制缺陷的形成、类型及变化已成为晶体材料领域研究的重要课题。
本文以Zn(NO_3)_2·6H_2O、尿素为原料,通过燃烧法,实现纳米ZnO的瞬态氮掺杂。在此基础上对晶体缺陷化学—热力学公式和晶体化学原理进行理论上研究,计算理论绝热燃烧火焰温度,完成了氮掺杂纳米氧化锌的优化设计。
通过X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)、红外光谱(IR)、光电子能谱(XPS)对粉体进行表征,研究制备过程中影响纳米氮掺杂ZnO性能的各种因素,借助差热分析对制备机理进行探讨。在此基础上,通过对氮掺杂纳米ZnO的偶联剂改性,获得稳定的氮掺杂纳米ZnO分散乳液。参照FZ/T 73023—2006中国人民共和国纺织行业标准——抗菌针织品及AATCC 183-2004紫外辐射通过织物的透射或阻挡性能,系统研究了氮掺杂纳米ZnO对纺织品的抗菌、防紫外性能。
主要研究工作和成果如下:
①瞬态氮掺杂过程中,尿素既是燃料为掺杂反应提供能量,又是氮源。同时分解所释放气体的膨胀效应,实现了微晶间的有效阻聚。完成了传统工艺中制备、陈化、洗涤、干燥、煅烧、研磨等多道工序的减并,制备出高性能氮掺杂纳米级粉色ZnO粉体。
②利用热力学公式对理论绝热燃烧火焰温度进行了计算,得到最佳工艺优化:燃料与物料摩尔比4.920;环境温度800℃;Zn(NO_3)_2·6H_2O水溶液的浓度60g/L。通过此种工艺所得到的粉体综合性能最好,平均粒度为30nm,氮掺量为1.02%,晶相与标准立方相ZnO衍射峰完全一致,没有其他杂相出现,颜色为均匀的粉色。
③改性过程中,以多羟基化合物三乙醇胺为桥基,对氮掺杂纳米ZnO进行表面预修饰,增加纳米粒子表面的羟基基团,在水介质中采用球磨工艺实施硅烷偶联剂改性,减少分散过程的软团聚,获得高浓度氮掺杂纳米ZnO水性分散浆料。
④经氮掺杂纳米ZnO整理过的棉织物,紫外防护因子测试结果表明:UPF指数从4.5提升至52,并具有较好的水洗牢度,水洗20次仍然保持同样的抗紫外性。
⑤抗菌性不受环境影响,即使在无光情况下也表现出极好的抗菌性能,且抑菌圈、抑菌率实验及氮掺杂纳米氧化锌整理后的织物抑菌率达到99%。并结合琼脂球面扩散动力学理论,指导抑菌圈实际测试,解释氮掺杂纳米ZnO抑菌机理。
本文首次提出利用燃烧法完成纳米ZnO的瞬态氮掺杂,实现传统工艺中制备、陈化、洗涤、干燥、煅烧、研磨等多道工序的减并,具有节能、降耗、减排的优点。氮掺杂纳米ZnO在纺织领域的应用填补了该产品在纺织领域的应用空白,为纺织用抗菌、抗紫外功能剂提供了新品种。
Recently, much attention has been focused on the modification of nanocrystallite metal oxide by doping or substituting with special atom. With such modification, it is possible to improve the electrical and optical properties of materials by changing the surface properties, such as electronic band gap, O vacancies, crystal deficiencies and specific surface area (SSA).
In the paper, N-doped ZnO (ZNO) nanocrystalline were synthesized by deflagration method using urea as main fuel, surfactant as assistant fuel and zinc nitrate as oxidant. The variation of adiabatic flame temperature (Tad) with the various fuel-to-oxidizer molar ratios value was calculated theoretically according to the thermodynamic concept. The effects of environment temperature, molar ratio of urea-to-zinc nitrate and combustion time on the properties of nanopowder were investigated. XRD, FTIR, SEM, TEM and XPS were used to characterize the properties of the as-synthesized samples. The ultraviolet prevention and antimicrobial properties on cotton fabrics treated by N-doped nano-ZnO were studied.
The main research work and results are as follows:
(1) During preparing N-doped nano-ZnO, The action of urea not only offered the energy, but also was the source of nitrogen. The effective inhibition effect between crystallites was realized by the expansion effect of gas released by urea. The combustion is a simplification of multi-procedures, such as traditional preparation, aging, dryinh, calcinating processes and rubbing. The N-doped ZnO (ZNO) nanocrystalline with excellent performance were synthesized by this method.
(2) The variation of adiabatic flame temperature (Tad) with the various fuel-to-oxidizer molar ratios value was calculated theoretically according to the thermodynamic concept. The experimental results show that perfect pink powders with standard cubic ZnO crystal phase are obtained under 800℃when the urea-to-zinc nitrate molar ratio is 4.920 and the concentration of the zinc nitrate is 60g/L.The average primary granularity of the as-synthsized sample is about 30 nm estimated according to Scherrer Equation. The analysises of XPS indicates that the concentrantion of N-doped in the sample is 1.02%.
(3) In this paper, well-dispersed N-doped ZnO (ZNO) nanocrystalline slurry in water medium with high concentration was prepared through the coordination action using silane coupling agent and multi-hydroxy compound. The results reveal that the N-doped ZnO (ZNO) nanocrystalline modified by multi-hydroxy compound in advance has strong combination ability with silane couple agent. Modified N-doped ZnO (ZNO) nanocrystalline has small size, even distribution and well-disperse stability.
(4) UPF test results indicate the perfect ultraviolet prevention, A high washing fastness is also attained. The index of UPF is from 4.5 to 52.
(5) The antibacterium-circle test indicate the broad-spectrum antibacterial activities. Specially, the antibacterial activities are very good even without light irradiation.
In this paper, the N-doped ZnO (ZNO) nanocrystalline with excellent performance were synthesized by combustion for the first time. The combustion is a simplification of multi-procedures, such as traditional preparation, aging, drying, calcinating processes and rubbing. Moreover, the systemic research about the antibacterium and ultraviolet prevention of the N-doped ZnO on textile was for the first. The excellent antibacterium and ultraviolet prevention properties will make N-doped ZnO nanocrystallites become a replaceable and cheap functional agent for textile.
引文
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